Polymer, process for producing the polymer, and curable composition containing the polymer

ABSTRACT

A vinyl polymer having, at a molecular chain terminus, a structure represented by the general formula 1: 
                         
(wherein R 3  is a hydroxy, amino, epoxy, carboxylic acid, ester, ether, amide or silyl group, an alkenyl group having low polymerizability, an organic compound having 1 to 20 carbon atoms, X is a halogen atom, a nitroxide or sulfide group or a cobalt porphyrin complex).

This application is a Divisional of U.S. Ser. No. 10/260,416 filed Oct.1, 2002, now U.S. Pat. No. 6,887,936 which is a Divisional of U.S. Ser.No. 09/509,095 filed Jun. 5, 2000, now U.S. Pat. No. 6,482,900, which isa National Phase of PCT/JP98/04520 filed Sep. 22, 1998.

TECHNICAL FIELD

The present invention relates to a vinyl polymer having a terminalfunctional group, a process of producing the same and a curablecomposition comprising said polymer.

BACKGROUND ART

Polymers having a terminal functional group are known to give curedproducts excellent in heat resistance and durability, among others, uponcrosslinking either by themselves or in combination with an appropriatecuring agent. Typical examples among them are alkenyl-, hydroxy- orcrosslinkable silyl-terminated polymers. Alkenyl-terminated polymers arecrosslinked and cure upon use, as a curing agent, of ahydrosilyl-containing compound or upon application of a photochemicalreaction. Hydroxy-terminated polymers, when reacted with apolyisocyanate, form a urethane bond and cure. Crosslinkablesilyl-terminated polymers, when they absorb moisture in the presence ofan appropriate condensation catalyst, give cured products.

As examples of the main chain skeleton of such alkenyl-, hydroxy- orcrosslinkable silyl-terminated polymers, there may be mentioned, amongothers, polyether polymers such as polyethylene oxide, polypropyleneoxide and polytetramethylene oxide; hydrocarbon polymers such aspolybutadiene, polyisoprene, polychloroprene, polyisobutylene, andhydrogenation products derived from these; and polyester polymers suchas polyethylene terephthalate, polybutylene terephthalate andpolycaprolactone. Such polymers are used in various applicationsdepending on the main chain skeleton and the mode of crosslinking.

Apart from those polymers illustrated above which are obtainable byionic polymerization or polycondensation, those vinyl polymers having aterminal functional group which are obtainable by radical polymerizationhave scarcely been put to practical use. Among vinyl polymers,(meth)acrylic polymers have high weathering resistance and transparency,among others, which cannot be expected of the above-mentioned polyetherpolymers, hydrocarbon polymers or polyester polymers, and those havingalkenyl or crosslinkable silyl groups on side chains are used in highweathering resistance paint compositions and the like. On the otherhand, the polymerization control of vinyl polymers is not easy owing toside reactions and it is very difficult to introduce a functional groupterminally thereinto.

If vinyl polymers having a functional group at a molecular chainterminus can be obtained in a simple and easy manner, there will beobtained cured products excellent in physical properties as comparedwith those having an alkenyl group on side chains. For that reason,investigations have been so far made by a large number of researchers todevelop a process for producing them. However, it is still not easy toproduce them on a commercial scale.

In Japanese Kokai Hei-05-255415 is disclosed a process of synthesizing(meth)acrylic polymers having an alkenyl group at both termini by usingan alkenyl-containing disulfide as a chain transfer agent and, inJapanese Kokai Hei-05-262808, there is disclosed a process ofsynthesizing (meth)acrylic polymers having an alkenyl group at bothtermini which comprises synthesizing a (meth)acrylic polymer having ahydroxy group at both termini using a hydroxy-containing disulfide andthen introducing an alkenyl group at both termini by utilizing thereactivity of the hydroxy group. However, it is not easy to introduce analkenyl group into both termini with certainty by these processes. Forterminally introducing a functional group with certainty, the chaintransfer agent must be used in a large amount, which raises a problemfrom the production process viewpoint.

Separately, the present inventors have already invented a process ofintroducing an olefin group terminally into a vinyl polymer by adding,after polymerization of a vinyl polymer, a compound having apolymerizable alkenyl group and an alkenyl group low in polymerizabilityto thereby reacting the polymerizable alkenyl group with the polymerterminus. By this process, however, it is not easy to introduce only oneolefin into a terminus with certainty even when the polymerizationproceeds in a living mode. In particular, addition of the olefin at astage at which the polymerizable monomer still remains results in randomcopolymerization, which makes it more difficult to control thestructure.

Accordingly, the present invention has an object to have a vinyl polymerhaving a terminal functional group, a process for producing the same anda curable composition comprising said polymer.

It is known that, generally, unactivated olefins, such as α-olefins, isnot polymerized in the manner of radical polymerization. The same alsoapplies to living radical polymerization, which has recently beeninvestigated actively.

As a result of intensive investigations, the present inventors foundthat when an inactivated (low polymerizability) olefin is added to aliving radical polymerization system, approximately one molecule aloneadds to the growing terminus and, by utilizing this finding, invented aprocess for producing polymers having various terminal functionalgroups.

SUMMARY OF THE INVENTION

A first aspect of the present invention is concerned with a vinylpolymer having, at a molecular chain terminus, a structure representedby the general formula 1:

wherein R³ is a hydroxy, amino, epoxy, carboxylic acid, ester, ether,amide or silyl group, a group represented by the general formula 2:

in which R⁴ is a hydrogen atom or a methyl group, or a polymerizableolefin-free organic group containing 1 to 20 carbon atoms,

R¹ is a divalent hydrocarbon group containing 1 to 20 carbon atoms or agroup having a structure represented by the general formula 3:

in which R⁵ is an oxygen atom, a nitrogen atom or an organic groupcontaining 1 to 20 carbon atoms, R⁶ is a hydrogen atom or a methyl groupand each may be the same or different,

and R² is a hydrogen atom or a methyl group and X is a halogen,nitroxide or sulfide group or a cobalt porphyrin complex.

The vinyl polymer having a terminal functional group according to thepresent invention can be produced by adding a functionalgroup-containing olefin compound having low polymerizability to a livingradical polymerization system during polymerization or after completionof the polymerization.

The functional group-containing olefin compound having lowpolymerizability is represented by the general formula 4:

wherein R³ is a hydroxy, amino, epoxy, carboxylic acid, ester, ether,amide or silyl group, a group represented by the general formula 2:

in which R⁴ is a hydrogen atom or a methyl group, or a polymerizableolefin-free organic group containing 1 to 20 carbon atoms,

R¹ is a divalent hydrocarbon group containing 1 to 20 carbon atoms or agroup having a structure represented by the general formula 3:

in which R⁵ is an oxygen atom, a nitrogen atom or an organic groupcontaining 1 to 20 carbon atoms, R⁶ is a hydrogen atom or a methyl groupand each may be the same or different,

and R² is a hydrogen atom or a methyl group.

The vinyl polymer having a terminal functional group according to thepresent invention has a feature that a molecular weight distribution isnarrow.

The vinyl polymer having a terminal functional group according to thepresent invention can be used by adding a curing agent thereto accordingto need, for preparing a curable composition comprising said vinylmonomer.

DETAILED DESCRIPTION OF THE INVENTION

Vinyl Polymer Having a Functional Group at Termini

The vinyl polymer having a terminal structure represented by the generalformula 1 comprises approximately one terminal group in question boundto each polymer terminus directly via a carbon-carbon bond, without theintermediary of a hetero atom:

wherein R³ is a hydroxy, amino, epoxy, carboxylic acid, ester, ether,amide or silyl group, a group represented by the general formula 2:

(in which R⁴ is a hydrogen atom or a methyl group) or a polymerizableolefin-free organic group containing 1 to 20 carbon atoms, R¹ is adivalent hydrocarbon group containing 1 to 20 carbon atoms or a grouphaving a structure represented by the general formula 3:

(in which R⁵ is an oxygen atom, a nitrogen atom or an organic groupcontaining 1 to 20 carbon atoms, R⁶ is a hydrogen atom or a methyl groupand each may be the same or different), R² is a hydrogen atom or amethyl group and X is a halogen, nitroxide or sulfide group or a cobaltporphyrin complex.

As specific examples of R¹ in the general formula 1, there may bementioned the following:

—(CH₂)_(n)— (n being an integer of 1 to 20),

—CH(CH₃)—, —CH(CH₂CH₃)—, —C(CH₃)₂—, —C(CH₃)(CH₂CH₃)—, —C(CH₂CH₃)₂—,—CH₂CH(CH₃)—, —(CH₂)_(n)—O—CH₂— (n being an integer of 1 to 19),

—CH(CH₃)—O—CH₂—, —CH(CH₂CH₃)—O—CH₂—, —C(CH₃)₂—O—CH₂—,—C(CH₃)(CH₂CH₃)—O—CH₂—, —C(CH₂CH₃)₂—O—CH₂—, —(CH₂)_(n)—O—(CH₂)_(m)— (mand n each being an integer of 1 to 19, with the condition 2≦m+n≦20),

—(CH₂)_(n)—C(O)O—(CH₂)_(m)— (m and n each being an integer of 1 to 19,with the condition 2≦m+n≦20),

—(CH₂)_(n)—OC(O)—(CH₂)_(m)—C(O)O—(CH₂)_(l)— (l being an integer of 0 to18 and m and n each being an integer of 1 to 17, with the condition2≦l+m+n≦18),

—(CH₂)_(n)-o-,m-,p-C₆H₄—, —(CH₂)_(n)—o—,m-,p-C₆H₄—(CH₂)_(m)— (m being aninteger of 0 to 13 and n being an integer of 1 to 14, with the condition1≦m+n≦14),

—(CH₂)_(n)-o-,m-,p-C₆H₄—O—(CH₂)_(m)— (m being an integer of 0 to 13 andn being an integer of 1 to 14, with the condition 1≦m+n≦14),

—(CH₂)_(n)-o-,m-,p-C₆H₄—O—CH(CH₃)— (n being an integer of 1 to 12),

—(CH₂)_(n)-o-,m-,p-C₆H₄—O—CH(CH₃)₂— (n being an integer of 1 to 11),

—(CH₂)_(n)—o—,m-,p-C₆H₄—C(O)O—(CH₂)_(m)— (m and n each being an integerof 1 to 12, with the condition 2≦m+n≦13),

—(CH₂)_(n)—OC(O)-o-,m-p-C₆H₄—C(O)O—(CH₂)_(m)— (m and n each being aninteger of 1 to 11, with the condition 2≦m+n≦12),

—(CH₂)_(n)-o-,m-,p-C₆H₄—OC(O)—(CH₂)_(m)— (m and n each being an integerof 1 to 12, with the condition 2≦m+n≦13),

—(CH₂)_(n)—C(O)O-o-,m-,p-C₆H₄—(CH₂)_(m)— (m and n each being an integerof 1 to 11, with the condition 2≦m+n≦12), and the like.

In the general formula 1, R² is a hydrogen atom or a methyl group,preferably a hydrogen atom. X is a halogen, nitroxide or sulfide groupor a cobalt porphyrin complex. From the ease of production viewpoint, Xis preferably a halogen group, in particular bromo.

As examples of R³ in the general formula 1, there may be mentioned thefollowing:

wherein R⁷ is a hydrocarbon group containing 1 to 20 carbon atoms, R⁹and R¹⁰ each is an alkyl group containing 1 to 20 carbon atoms, an arylgroup containing 6 to 20 carbon atoms, an aralkyl group containing 7 to20 carbon atoms or a triorganosiloxy group represented by (R′)₃SiO— (inwhich R′ is a monovalent hydrocarbon group containing 1 to 20 carbonatoms and the three R′ groups may be the same or different) and; whentwo or more R⁹ or R¹⁰ groups are present, they may be the same ordifferent, Y represents a hydroxy group or a hydrolyzable group and,when two or more Y groups are present, they may be the same ordifferent; a represents 0, 1, 2 or 3, b represents 0, 1 or 2 and m is aninteger of 0 to 19, with the condition a+mb≧1.

As specific examples of R⁷, there may be mentioned the following:

-   —(CH₂)_(n)—CH₃,-   —CH(CH₃)— (CH₂)_(n)—CH₃,-   —CH(CH₂CH₃)— (CH₂)_(n)—CH₃,-   —CH(CH₂CH₃)₂,-   —C(CH₃)₂—(CH₂)_(n)—CH₃,-   —C(CH₃)(CH₂CH₃)— (CH₂)_(n)—CH₃,-   —C₆H₅,-   —C₆H₅ (CH₃),-   —C₆H₅(CH₃)₂,-   —(CH₂)_(n)—C₆H₅—,-   —(CH₂)_(n)—C₆H₅ (CH₃),-   —(CH₂)_(n)—C₆H₅(CH₃)₂    wherein n is an integer not smaller than 0 and the total number of    carbon atoms is not more than 20.

The hydrolyzable group represented by Y is not particularly restrictedbut may be any of those known in the art. Specifically, there may bementioned a hydrogen, halogen atom, and alkoxy, acyloxy, ketoximate,amino, amide, acid amide, aminoxy, mercapto, alkenyloxy and like groups.From the viewpoint of mild hydrolyzability and easy handling, alkoxygroups are particularly preferred. One to three such hydrolyzable and/orhydroxy groups can be bound to one silicon atom and the total number ofhydrolyzable groups, namely a+mb, is preferably within the range of 1 to5. When two or more hydrolyzable and/or hydroxy groups are present inthis silyl group, they may be the same or different. The number ofsilicon atoms constituting this silicon group may be one, two or moreand, in the case of silicon atoms connected by siloxane bonding, thenumber of silicon atoms may amount up to about 20.

The structure of R³ is not limited to those illustrated above but may beany of various structures. Preferred, however, are hydroxy, amino,epoxy, carboxylic acid, ester, ether, amide and silyl groups. Alkenylgroups represented by the general formula 2 are also preferred. Amongthem, alkenyl and hydroxy groups are particularly preferred. As regardsthe alkenyl groups, they are limited to those having no radicalpolymerizability in view of the production process. There are no otherparticular limitations. The term “silyl group” as used in the presentinvention means a silicon atom-containing group, and as preferredexamples thereof, there can be mentioned crosslinkable silyl groups andsilyl groups generally used as protective groups, among others.

In cases where there is an alkenyl group introduced terminally, noparticular limitations are imposed on the structure of the generalformula 1, although the following structure may be mentioned as apreferred example:

n is an integer of 1 to 20, preferably 2, 4 or 6, because of ready rawmaterial availability.

The number of terminal groups to be contained in each molecule of thevinyl polymer of the present invention is not particularly restrictedbut, in cases where said polymer is used in curable compositions, it ispreferred that two or more be contained.

The radical polymerizable olefin monomer constituting the main chain ofsaid vinyl polymer is not particularly restricted but includes variousspecies. As examples, there may be mentioned (meth)acrylic acid,methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate,isopropyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate,tert-butyl(meth)acrylate, n-pentyl(meth)acrylate, n-hexyl(meth)acrylate,cyclohexyl(meth)acrylate, n-heptyl(meth)acrylate, n-octyl(meth)acrylate,2-ethylhexyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate,dodecyl(meth)acrylate, phenyl(meth)acrylate, toluyl(meth)acrylate,benzyl(meth)acrylate, 2-methoxyethyl(meth)acrylate,3-methoxybutyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate,2-hydroxypropyl(meth)acrylate, stearyl(meth)acrylate,glycidyl(meth)acrylate, 2-aminoethyl(meth)acrylate,γ-(methacryloyloxy)propyltrimethoxysilane, (meth)acrylic acid-ethyleneoxide adducts, trifluoromethylmethyl(meth)acrylate,2-trifluoromethylethyl(meth)acrylate,2-perfluoroethylethyl(meth)acrylate,2-perfluoroethyl-2-perfluorobutylethyl(meth)acrylate,2-perfluoroethyl(meth)acrylate, perfluoromethyl(meth)acrylate,diperfluoromethylmethyl(meth)acrylate,2-perfluoromethyl-2-perfluoroethylmethyl(meth)acrylate,2-perfluorohexylethyl(meth)acrylate,2-perfluorodecylethyl(meth)acrylate,2-perfluorohexadecylethyl(meth)acrylate and like (meth)acrylic monomers;styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonicacid and salts thereof, and like styrenic monomers; perfluoroethylene,perfluoropropylene, vinylidene fluoride and like fluorine-containingvinyl monomers; vinyltrimethoxysilane, vinyltriethoxysilane and likesilicon-containing vinyl monomers; maleic anhydride, maleic acid, maleicacid monoalkyl esters and dialkyl esters; fumaric acid, fumaric acidmonoalkyl esters and dialkyl esters; maleimide, methylmaleimide,ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide,octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide,cyclohexylmaleimide and like maleimide monomers; acrylonitrile,methacrylonitrile and like nitrile group-containing vinyl monomers;acrylamide, methacrylamide and like amide group-containing vinylmonomers; vinyl acetate, vinyl propionate, vinyl pivalate, vinylbenzoate, vinyl cinnamate and like vinyl esters; ethylene, propylene andlike alkenes; butadiene, isoprene and like conjugated dienes; vinylchloride, vinylidene chloride, allyl chloride and allyl alcohol, amongothers. These may be used singly or a plurality of monomers may becopolymerized. Among them, styrenic monomers and (meth)acrylic monomersare preferred from the viewpoint of physical properties of products,among others. Further, from the viewpoint of high reactivity infunctional group introduction reaction in the practice of the presentinvention and of low glass transition temperature, among others, acrylicester monomers are more preferred and butyl acrylate is particularlypreferred.

The vinyl polymer of the present invention preferably has a molecularweight distribution, namely ratio (Mw/Mn) of weight average molecularweight (Mw) to number average molecular weight (Mn) as determined by gelpermeation chromatography, of less than 1.8, more preferably not morethan 1.6, most preferably not more than 1.3.

The vinyl polymer of the present invention preferably has a numberaverage molecular weight within the range of 500 to 100,000, morepreferably 3,000 to 40,000. When the molecular weight is not more than500, the characteristics intrinsic in the vinyl polymer can hardly beexpressed. A molecular weight not less than 100,000 makes handlingdifficult.

Method of Producing the Vinyl Polymer Having a Functional Group atTermini

The production process of the present invention comprises adding afunctional group-containing olefin compound having low polymerizabilityto a living radical polymerization system during polymerization or aftercompletion of the polymerization to thereby produce a vinyl polymerhaving a terminal functional group.

The “living radical polymerization” proceeds at a high rate ofpolymerization and hardly undergoes termination reactions and gives apolymer with a narrow molecular weight distribution (an Mw/Mn value ofabout 1.1 to 1.5) in spite of it being a radical polymerization which isregarded as difficult to control because of tendency toward occurrenceof termination reactions such as radical-to-radical coupling. It is alsopossible, in living radical polymerization, to arbitrarily control themolecular weight by adjusting the monomer/initiator charge ratio.

The “living radical polymerization” method thus can give a polymerhaving low viscosity and a narrow molecular weight distribution and, inaddition, allows introduction of the specific functionalgroup-containing monomer into the polymer mostly at the desired sitesand, therefore, is preferred as the production process the abovespecific functional group-containing vinyl polymer.

While the term “living polymerization”, in its narrower sense, meanspolymerization in which molecular chains grow while the termini thereofalways retain their activity, said term generally includes, within themeaning thereof, quasi-living polymerization in which terminallyinactivated molecules and terminally active molecules grow in a state ofequilibrium. The latter definition applies to the living polymerizationto be employed in the practice of the present invention.

Such “living radical polymerization” has recently been studied activelyby various groups of researchers. As examples, there may be mentioned,among others, the polymerization which uses a cobalt-porphyrin complexas described in J. Am. Chem. Soc., 1994, vol. 116, pages 7943 ff, thepolymerization which uses a radical capping agent such as a nitroxidecompound as described in Macromolecules, 1994, vol. 27, pages 7228 ff.,and “atom transfer radical polymerization (ATRP)” which uses an organichalide or the like as the initiator and a transition metal complex asthe catalyst.

Among the “living radical polymerization” techniques, theabove-mentioned “atom transfer radical polymerization” technique, whichuses an organic halide or halogenated sulfonyl compound or the like asthe initiator and a transition metal complex as the catalyst forpolymerizing vinyl monomers, has, in addition to the above-mentionedfeatures of “living radical polymerization”, features in that it gives apolymer having a halogen or the like, which is relatively advantageousto functional group conversion, at main chain termini and that thedegree of freedom in initiator and catalyst designing and, therefore, ismore preferred as the production process in the practice of the presentinvention. This atom transfer radical polymerization is described, forexample, by Matyjaszewski et al. in J. Am. Chem. Soc., 1995, vol. 117,pages 5614 ff.; Macromolecules, 1995, vol. 28, pages 7901 ff.; Science,1996, vol. 272, pages 866 ff.; WO 96/30421 and WO 97/18247, and bySawamoto et al. in Macromolecules, 1995, vol. 28, pages 1721 ff.

In the production process of the present invention, the use of the atomtransfer radical polymerization technique is preferred although thereare no particular restrictions as to which of the techniques mentionedabove is to be employed.

Among such living radical polymerization techniques, the technique whichuses a radical capping agent such as a nitroxide compound is firstdescribed. In this polymerization technique, a stable nitroxy freeradical (═N—O.) is generally used as a radical capping agent. Suchcompound is not restricted but is preferably a2,2,6,6-substituted-1-piperidinyloxy radical, a2,2,5,5-substituted-1-pyrrolidinyloxy radical or nitroxy free radicalderived from a cyclic hydroxyamine. Suitable as the substituents arealkyl groups containing not more than 4 carbon atoms, such as methyl orethyl. As specific nitroxy free radical compounds, they are notrestricted but include, among others,2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO),2,2,6,6-tetraethyl-1-piperidinyloxy radical,2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical,2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical,1,1,3,3-tetramethyl-2-isoindolinyloxy radical andN,N-di-t-butylamine-oxy radical. Such a stable free radical asgalvinoxyl free radical may be used in lieu of the nitroxy free radical.

Said radical capping agent is used in combination with a radicalgenerator. It is supposed that the reaction product from the radicalcapping agent and radical generator serve as a polymerization initiatorto thereby cause the polymerization of an addition-polymerizablemonomer(s) to proceed. The ratio between the amounts of both is notparticularly restricted but the radical initiator is judiciously used inan amount of 0.1 to 10 moles per mole of the radical capping agent.

While various compounds can be used as the radical generator, a peroxidecapable of generating a radical under polymerization temperatureconditions is preferred. Said peroxide is not restricted but includes,among others, diacyl peroxides such as benzoyl peroxide and lauroylperoxide; dialkyl peroxides such as dicumyl peroxides and di-t-butylperoxide; peroxycarbonates such as diisopropyl peroxydicarbonate andbis(4-t-butylcyclohexyl)peroxydicarboante; and alkyl peresters such astert-butyl peroxyoctoate and t-butyl peroxybenzoate. In particular,benzoyl peroxide is preferred. Further, such a radical generator as aradical generating azo compound, for example azobisisobutyronitrile, mayalso be used in lieu of the peroxide.

As reported in Macromolecules, 1995, vol. 28, pages 2993 ff.,alkoxyamine compounds such as illustrated below may be used in lieu ofthe combined use of a radical capping agent and a radical generator.

When an alkoxyamine compound is used as the initiator and when saidcompound is a hydroxy- or like functional group-containing one such asillustrated above, functional group-terminated polymers are obtained.

The polymerization conditions, e.g. monomer, solvent, polymerizationtemperature, etc., to be used in carrying out the polymerization usingthe above nitroxide compound or like radical capping agent are notrestricted but may be the same as those to be used in the atom transferradical polymerization described in the following.

The atom transfer radical polymerization technique, which is preferredas the living radical polymerization method to be used in the practiceof the present invention, is described in the following.

In this atom transfer radical polymerization, an organic halide, inparticular an organic halide having a highly reactive carbon-halogenbond (e.g. an ester compound having a halogen at α-position or acompound having a halogen at the benzyl site), or a halogenated sulfonylcompound is used as the initiator.

A metal complex containing an element of the group 7, 8, 9, 10 or 11 ofthe periodic table as a central metal atom is used as the catalyst.Preferred metal species are copper, nickel, ruthenium and iron, inparticular monovalent copper, divalent ruthenium and divalent iron arepreferred among others. In particular, copper is preferred. Specificexamples are cuprous chloride, cuprous bromide, cuprous iodide, cuprouscyanide, cuprous oxide, cuprous acetate, cuprous perchlorate and thelike. When a copper compound is used, a ligand, such as 2,2′-bipyridylor a derivative thereof, 1,10-phenanthroline or a derivative thereof, analkylamine such as tributylamine or a polyamine such astetramethylethylenediamine, pentamethyldiethylenetriamine orhexamethyltriethylenetetraamine, is added to enhance the catalyticactivity. A tristriphenylphosphine complex of divalent ruthenium(RuCl₂(PPh₃)₃) is also suited for use as the catalyst. When thiscatalyst is used, an aluminum compound such as a trialkoxyaluminum isadded for increasing the activity of said catalyst. Furthermore, atristriphenylphosphine complex of divalent iron (FeCl₂(PPh₃)₃) is alsosuited as the catalyst.

In this polymerization technique, an organic halide or a halogenatedsulfonyl compound is used as the initiator. Specific examples are, amongothers:

C₆H₅—CH₂X,

C₆H₅—C(H)(X)CH₃,

C₆H₅—C(X)(CH₃)₂ (in the above chemical formulas, C₆H₅ is a phenyl groupand X is chlorine, bromine or iodine);

R¹¹—C(H)(X)—CO₂R¹²,

R¹¹—C(CH₃)(X)—COR¹²,

R¹¹—C(H)(X)—C(O)R¹²,

R¹¹—C(CH₃)(X)—C(O)R¹² (in which R¹¹ and R¹² each is a hydrogen atom oran alkyl group having 1 to 20 carbon atoms, aryl group or aralkyl groupand X is chlorine, bromine or iodine); and

R¹¹—C₆H₄—SO₂X (in which R¹¹ is a hydrogen atom or an alkyl group having1 to 20 carbon atoms, aryl group or aralkyl group and X is chlorine,bromine or iodine).

When an organic halide or halogenated sulfonyl compound having afunctional group other than the functional group for initiatingpolymerization is used, polymers having the functional group introducedinto a terminus can easily be obtained. As such functional group, theremay be mentioned alkenyl, hydroxy, epoxy, amino, amide and silyl groups,among others.

The alkenyl-containing organic halide is not particularly restricted butmay be one having the structure shown by the general formula 7:R¹⁴R¹⁵C(X)—R¹⁶—R¹⁷—C(R¹³)═CH₂  (7)wherein R¹³ is a hydrogen atom or a methyl group, R¹⁴ and R¹⁵ each is ahydrogen atom or a monovalent alkyl group having 1 to 20 carbon atoms,aryl or aralkyl group and R¹⁴ and R¹⁵ may be bound to each other atrespective other termini, R¹⁶ is C(O)O— (ester group), —C(O)— (ketogroup) or an o-, m- or p-phenylene group, R¹⁷ is a direct bond or adivalent organic group having 1 to 20 carbon atoms, which may optionallycontain one or more ether bonds, and X is chlorine, bromine or iodine.

In these compounds, the carbon atom to which the halogen is bound isbound to a carbonyl or phenyl group, for instance, so that thecarbon-halogen bond is activated to initiate the polymerization.

As specific examples of the substituents R¹⁴ and R¹⁵, there may bementioned hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl,hexyl, etc. R¹⁴ and R¹⁵ may be bound to each other at respective othertermini to form a cyclic skeleton. In that case, —R¹⁴—R¹⁵— represents—CH₂CH₂—, —CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂— or —CH₂CH₂CH₂CH₂CH₂—, forinstance.

As specific examples of the alkenyl-containing organic haliderepresented by the general formula 7, there may be mentioned thefollowing:

XCH₂C(O)O(CH₂)_(n)CH═CH₂, H₃CC(H)(X)C(O)O(CH₂)_(n)CH═CH₂,

(H₃C)₂C(X)C(O)O(CH₂)_(n)CH═CH₂,

CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)CH═CH₂,

(in each formula mentioned above, X is chlorine, bromine or iodine and nis an integer of 0 to 20);XCH₂C(O)O(CH₂)_(n)O(CH₂)_(m)CH═CH₂,H₃CC(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(n)CH═CH₂,(H₃C)₂C(X)C(O)O(CH₂)_(n)O(CH₂)_(m)CH═CH₂,CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)CH═CH₂,

(in each formula mentioned above, X is chlorine, bromine or iodine, n isan integer of 1 to 20 and m is an integer of 0 to 20);o,m,p-XCH₂—C₆H₄—(CH₂)_(n)—CH═CH₂,o,m,p-CH₃C(H)(X)—C₆H₄—(CH₂)_(n)—CH═CH₂,o,m,p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)_(n)—CH═CH₂, (in each formula mentionedabove, X is chlorine, bromine or iodine and n is an integer of 0 to 20);o,m,p-XCH₂—C₆H₄—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂,o,m,p-CH₃C(H)(X)—C₆H₄—(CH₂)_(n)—(CH₂)_(m)—CH═CH₂,o,m,p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂, (in each formulamentioned above, X is chlorine, bromine or iodine, n is an integer of 1to 20 and m is an integer of 0 to 20);o,m,p-XCH₂—C₆H₄—O—(CH₂)_(n)—CH═CH₂,o,m,p-CH₃C(H)(X)—C₆H₄—O—(CH₂)_(n)—CH═CH₂,o,m,p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)_(n)—CH═CH₂, (in each formula mentionedabove, X is chlorine, bromine or iodine and n is an integer of 0 to 20);o,m,p-XCH₂—C₆H₄—O—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂,o,m,p-CH₃C(H)(X)—C₆H₄—O—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂,o,m,p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂, (in eachformula mentioned above, X is chlorine, bromine or iodine, n is aninteger of 1 to 20 and m is an integer of 0 to 20);

As the alkenyl-containing organic halide, there may further be mentionedcompounds represented by the general formula 8:H₂C═C(R¹³)—R¹⁷—C(R¹⁴)(X)—R¹⁸—R¹⁵  (8)wherein R¹³, R¹⁴, R¹⁵, R¹⁷ and X are defined above and R¹⁸ is a directbond, —C(O)O— (ester group), —C(O)— (keto group) or an o-, m- orp-phenylene group.

R¹⁷ is a direct bond or a divalent organic group having 1 to 20 carbonatoms (which may optionally contain one or more ether bonds) and, whenit is a direct bond, the vinyl group is bound to the carbon to which thehalogen is bound, to form an allyl halide. In this case, thecarbon-halogen bond is activated by the neighboring vinyl group, so thatit is not always necessary for R¹⁸ to be a C(O)O group or a phenylenegroup, for instance but it may be a direct bond. When R¹⁷ is not adirect bond, R¹⁸ is preferably a C(O)O group, C(O) group or phenylenegroup so that the carbon-halogen bond may be activated.

Specific examples of the compound of the general formula 8 are, amongothers, the following:

CH₂═CHCH₂X, CH₂═C(CH₃)CH₂X, CH₂═CHC(H)(X)CH₃,

CH₂═C(CH₃)C(H)(X)CH₃, CH₂═CHC(X)(CH₃)₂, CH₂═CHC(H)(X)C₂H₅,

CH₂═CHC(H)(X)CH(CH₃)₂, CH₂═CHC(H)(X)C₆H₅, —CH₂═CHC(H)(X)CH₂C₆H₅,

CH₂═CHCH₂C(H)(X)—CO₂R, CH₂═CH(CH₂)₂C(H)(X)—CO₂R,

CH₂═CH(CH₂)₃C(H)(X)—CO₂R, CH₂═CH(CH₂)₈C(H)(X)—CO₂R,

CH₂═CHCH₂C(H)(X)—C₆H₅, CH₂═CH(CH₂)₂C(H)(X)—C₆H₅,

CH₂═CH(CH₂)₃C(H)(X)—C₆H₅ (in each formula mentioned above, X ischlorine, bromine or iodine and R is an alkyl group having 1 to 20carbon atoms, aryl group or aralkyl group).

Specific examples of the alkenyl-containing halogenated sulfonylcompound are as follows:

o,m,p-CH₂═CH—(CH₂)_(n)—C₆H₄—SO₂X and

o,m,p-CH₂═CH— (CH₂)_(n)—O—C₆H₄—SO₂X (in each formula mentioned above, Xis chlorine, bromine or iodine and n is an integer of 0 to 20), and thelike.

In the case of an alkenyl-containing initiator, the olefin of saidinitiator may possibly react with the polymerization termini, so thatcare should be exercised in selecting the polymerization conditions andthe conditions for the reaction with the olefin compound to be added. Asa specific example, there may be mentioned the addition of the olefincompound at an early stage of polymerization.

The crosslinkable silyl-containing organic halide is not particularlyrestricted but includes, among others, those having a structure shown bythe general formula 9:R¹⁴R¹⁵C(X)—R¹⁶—R¹⁷—C(H)(R¹³)CH₂—[Si(R⁹)_(2-b)(Y)_(b)O]_(m)—Si(R¹⁰)_(3-a)(Y)_(a)  (9)wherein R⁹, R¹⁰, R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, a, b, m, X and Y are asdefined above.

Specific examples of the compound of the general formula 9 are asfollows:

XCH₂C(O)O(CH₂)_(n)Si(OCH₃)₃, CH₃C(H)(X)C(O)O(CH₂)_(n)Si(OCH₃)₃,

(CH₃)₂C(X)C(O)O(CH₂)_(n)Si(OCH₃)₃,

XCH₂C(O)O(CH₂)_(n)Si(CH₃)(OCH₃)₂,

CH₃C(H)(X)C(O)O(CH₂)_(n)Si(CH₃)(OCH₃)₂,

(CH₃)₂C(X)C(O)O(CH₂)_(n)Si(CH₃) (OCH₃)₂ (in each formula mentionedabove, X is chlorine, bromine or iodine and n is an integer of 0 to 20);

XCH₂C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,

H₃CC(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,

(H₃C)₂C(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,

CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,

XCH₂C(O)O(CH₂)_(n)O(CH₂)_(m)Si(CH₃)(OCH₃)₂,

H₃CC(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)—Si(CH₃)(OCH₃)₂,

(H₃C)₂C(X)C(O)O(CH₂)_(n)O(CH₂)_(m)—Si(CH₃)(OCH₃)₂,

CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)—Si(CH₃) (OCH₃)₂ (in each formulamentioned above, X is chlorine, bromine or iodine, n is an integer of 1to 20 and m is an integer of 0 to 20);

o,m,p-XCH₂—C₆H₄— (CH₂)₂Si(OCH₃)₃,

o,m,p-CH₃C(H)(X)—C₆H₄—(CH₂)₂Si(OCH₃)₃,

o,m,p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)₂Si(OCH₃)₃,

o,m,p-XCH₂—C₆H₄—(CH₂)₃Si(OCH₃)₃,

o,m,p-CH₃C(H)(X)—C₆H₄—(CH₂)₃Si(OCH₃)₃,

o,m,p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)₃Si(OCH₃)₃,

o,m,p-XCH₂—C₆H₄—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,

o,m,p-CH₃C(H)(X)—C₆H₄—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,

o,m,p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,

o,m,p-XCH₂—C₆H₄—O—(CH₂)₃Si(OCH₃)₃,

o,m,p-CH₃C(H)(X)—C₆H₄—O—(CH₂)₃Si(OCH₃)₃,

o,m,p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)₃—Si(OCH₃)₃,

o,m,p-XCH₂—C₆H₄—O—(CH₂)₂—O—(CH₂)₃—Si(OCH₃)₃,

o,m,p-CH₃C(H)(X)—C₆H₄—O—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,

o,m,p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃ (in each formulamentioned above, X is chlorine, bromine or iodine), and the like.

As further examples of the crosslinkable silyl-containing organichalide, there may be mentioned those having a structure represented bythe general formula 10:(R¹⁰)_(3-a)(Y)_(a)Si—[OSi(R⁹)_(2-b)(Y)_(b)]_(m)—CH₂—C(H)(R¹³)—R¹⁷—C(R¹⁴)(X)—R¹⁸—R¹⁵  (10)wherein R⁹, R¹⁰, R¹³, R¹⁴, R¹⁵, R¹⁷, R¹⁸, a, b, m, X and Y are asdefined above.

Specific examples of such compound are as follows:

(CH₃O)₃SiCH₂CH₂C(H)(X)C₆H₅,

(CH₃O)₂(CH₃)SiCH₂CH₂C(H)(X)C₆H₅,

(CH₃O)₃Si(CH₂)₂C(H)(X)—CO₂R,

(CH₃O)₂(CH₃)Si(CH₂)₂C(H)(X)—CO₂R,

(CH₃O)₃Si(CH₂)₃C(H)(X)—CO₂R,

(CH₃O)₂(CH₃)Si(CH₂)₃C(H)(X)—CO₂R,

(CH₃O)₃Si(CH₂)₄C(H)(X)—CO₂R,

(CH₃O)₂(CH₃)Si(CH₂)₄C(H)(X)—CO₂R,

(CH₃O)₃Si(CH₂)₉C(H)(X)—CO₂R,

(CH₃O)₂(CH₃)Si(CH₂)₉C(H)(X)—CO₂R,

(CH₃O)₃Si(CH₂)₃C(H)(X)—C₆H₅,

(CH₃O)₂(CH₃)Si(CH₂)₃C(H)(X)—C₆H₅,

(CH₃O)₃Si(CH₂)₄C(H)(X)—C₆H₅,

(CH₃O)₂(CH₃)Si(CH₂)₄C(H)(X)—C₆H₅ (in each formula mentioned above, X ischlorine, bromine or iodine and R is an alkyl group having 1 to 20carbon atoms, aryl group or aralkyl group) and the like.

The hydroxy-containing organic halide or halogenated sulfonyl compoundis not particularly restricted but includes, among others, compoundsmentioned below:

-   HO—(CH₂)_(n)—OC(O)C(H)(R)(X)    wherein X is chlorine, bromine or iodine, R is a hydrogen atom, an    alkyl having 1 to 20 carbon atoms, an aryl group or an aralkyl group    and n is an integer of 1 to 20.

The amino-containing organic halide or halogenated sulfonyl compound isnot particularly restricted but includes, among others, compoundsmentioned below:

-   H₂N—(CH₂)_(n)—OC(O)C(H)(R)(X)    wherein X is chlorine, bromine or iodine, R is a hydrogen atom, an    alkyl having 1 to 20 carbon atoms, an aryl group or an aralkyl group    and n is an integer of 1 to 20.

The epoxy-containing organic halide or halogenated sulfonyl compound isnot particularly restricted but includes, among others, compoundsmentioned below:

wherein X is chlorine, bromine or iodine, R is a hydrogen atom, an alkylhaving 1 to 20 carbon atoms, an aryl group or an aralkyl group and n isan integer of 1 to 20.

For obtaining polymers having two or more terminal structuresrepresented by the general formula 1 within each molecule, an organichalide or halogenated sulfonyl compound having two or more initiationsites is used as the initiator. Specific examples are:

(in which C₆H₄ represents a phenylene group, X is chlorine, bromine oriodine, R is an alkyl group containing 1 to 20 carbon atoms, an arylgroup or an aralkyl group, and n is an integer of 0 to 20) and the like.

The radical polymerizable olefin monomer to be used in thispolymerization is not particularly restricted but includes those variousspecies already mentioned hereinabove. Since the polymerization systemshown herein is a living polymerization system, it is also possible toproduce block copolymers by successive addition of polymerizablemonomers.

The polymerization can be carried out in the absence or presence ofvarious solvents. The solvent species are not particularly restricted,however as an example thereof, there may be mentioned, hydrocarbonsolvents such as benzene and toluene; ether solvents such as diethylether and tetrahydrofuran; halogenated hydrocarbon solvents such asmethylene chloride and chloroform; ketone solvents such as acetone,methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such asmethanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butylalcohol; nitrile solvents such as acetonitrile, propionitrile andbenzonitrile; ester solvents such as ethyl acetate and butyl acetate;and carbonate solvents such as ethylene carbonate and propylenecarbonate. These may be used singly or two or more of them may be usedin admixture.

The polymerization can be conducted within the temperature range of roomtemperature to 200° C., preferably 50° C. to 150° C.

Upon addition of the functional group-containing olefin compound havinglow polymerizability, during such living radical polymerization or atthe end point thereof, approximately one molecule adds to each terminusand, as a result, the functional group of said olefin compound isintroduced terminally into the polymer. The end point of polymerizationis the time point at which preferably not less than 80%, more preferablynot less than 90%, particularly not less than 95%, most preferably notless than 99%, of the monomers have reacted.

The functional group-containing olefin compound having lowpolymerizability is selected from among compounds represented by thegeneral formula 4:

wherein R³ is a hydroxy, amino, epoxy, carboxylic acid, ester, ether,amide or silyl group, a group represented by the general formula 2:

wherein R⁴ represents a hydrogen atom or a methyl group, or apolymerizable olefin-free organic group containing 1 to 20 carbon atoms,R¹ is a divalent hydrocarbon group containing 1 to 20 carbon atoms or agroup having a structure of the general formula 3:

(in which R⁵ is an oxygen atom or nitrogen atom or an organic groupcontaining 1 to 20 carbon atoms, R⁶ is a hydrogen atom or a methyl groupand each may be the same or different) and R² is a hydrogen atom or amethyl group.

As specific examples of R¹ in the general formula 4, there may bementioned:

-   —(CH₂)_(n)— (n being an integer of 1 to 20),-   —CH(CH₃)—, —CH(CH₂CH₃)—, —C(CH₃)₂—, —C(CH₃)(CH₂CH₃)—, —C(CH₂CH₃)₂—,    —CH₂CH(CH₃)—, —(CH₂)_(n)—O—CH₂— (n being an integer of 1 to 19),-   —CH(CH₃)—O—CH₂—, —CH(CH₂CH₃)—O—CH₂—, —C(CH₃)₂—O—CH₂—,    —C(CH₃)(CH₂CH₃)—O—CH₂—, —C(CH₂CH₃)₂—O—CH₂—, —(CH₂)_(n)—O—(CH₂)_(m)—    (m and n each being an integer of 1 to 19, with the condition    2≦m+n≦20),-   —(CH₂)_(n)—C(O)O—(CH₂)_(m)— (m and n each being an integer of 1 to    19, with the condition 2≦m+n≦20),-   —(CH₂)_(n)—OC(O)—(CH₂)_(m)—C(O)O—(CH₂)_(l)— (1 being an integer of 0    to 18 and m and n each being an integer of 1 to 17, with the    condition 2≦l+m+n≦18),-   —(CH₂)_(n)-o-,m-,p-C₆H₄—, —(CH₂)_(n)-o-,m-,p-C₆H₄—(CH₂)_(m)—, (m    being an integer of 0 to 13 and n being an integer of 1 to 14, with    the condition 1≦m+n≦14),-   —(CH₂)_(n)-o-,m-,p-C₆H₄—O—(CH₂)_(m)— (m being an integer of 0 to 13    and n being an integer of 1 to 14, with the condition 1≦m+n≦14),-   —(CH₂)_(n)-o-,m-,p-C₆H₄—O—CH(CH₃)— (n being an integer of 1 to 12),-   —(CH₂)_(n)-o-,m-,p-C₆H₄—O—CH(CH₃)₂— (n being an integer of 1 to 11),-   —(CH₂)_(n)-o-,m-,p-C₆H₄—C(O)O—(CH₂)_(m)— (m and n each being an    integer of 1 to 12, with the condition 2≦m+n≦13),-   —(CH₂)_(n)—OC(O)-o-,m-,p-C₆H₄—C(O)O—(CH₂)_(m)— (m and n each being    an integer of 1 to 11, with the condition 2≦m+n≦12),-   —(CH₂)_(n)-o-,m-,p-C₆H₄—OC(O)—(CH₂)_(m)— (m and n each being an    integer of 1 to 12, with the condition 2≦m+n≦13),-   —(CH₂)_(n)—C(O)O-o-,m-,p-C₆H₄—(CH₂)_(m)— (m and n each being an    integer of 1 to 11, with the condition 2≦m+n≦12), etc.

R² in the general formula 4 is a hydrogen atom or a methyl group,preferably a hydrogen atom.

As examples of R³ in the general formula 4, there may be mentioned,among others, the following groups:

wherein R⁷ is a hydrocarbon group containing 1 to 20 carbon atoms; R⁹and R¹⁰ each is an alkyl group containing 1 to 20 carbon atoms, an arylgroup containing 6 to 20 carbon atoms, an aralkyl group containing 7 to20 carbon atoms or a triorganosiloxy group represented by (R′)₃SiO— (R′being a monovalent hydrocarbon group containing 1 to 20 carbon atoms andthe three R′ groups may be the same or different) and, when two or moreR⁹ or R¹⁰ groups are present, they may be the same or different; Yrepresents a hydroxy group or a hydrolyzable group and, when two or moreY groups are present, they may be the same or different; a represents 0,1, 2 or 3, b represents 0, 1 or 2 and m is an integer of 0 to 19, withthe condition that the relation a+mb≧1 should be satisfied.

As R⁷, the following groups may specifically be mentioned, among others:

—(CH₂)_(n)—CH₃,

—CH(CH₃)— (CH₂)_(n)—CH₃,

—CH(CH₂CH₃)—(CH₂)_(n)—CH₃,

—CH(CH₂CH₃)₂,

—C(CH₃)₂—(CH₂)_(n)—CH₃,

—C(CH₃)(CH₂CH₃)—(CH₂)_(n)—CH₃,

—C₆H₅,

—C₆H₅(CH₃),

—C₆H₅(CH₃)₂,

—(CH₂)_(n)—C₆H₅,

—(CH₂)_(n)—C₆H₅ (CH₃),

—(CH₂)_(n)—C₆H₅(CH₃)₂ (n being an integer not smaller than 0 and thetotal number of carbon atoms in each group being not more than 20).

The hydrolyzable group represented by Y is not particularly restrictedbut may be any of those known in the art. Specifically, there may bementioned a hydrogen, halogen atom, and alkoxy, acyloxy, ketoximate,amino, amide, acid amide, aminoxy, mercapto, alkenyloxy and like groups.From the viewpoint of mild hydrolyzability and easy handling, alkoxygroups are particularly preferred. One to three such hydrolyzable and/orhydroxy groups can be bound to one silicon atom and the total number ofhydrolyzable groups, namely a+mb, is preferably within the range of 1 to5. When two or more hydrolyzable and/or hydroxy groups are present inthis silyl group, they may be the same or different. The number ofsilicon atoms constituting this silicon group may be one, two or moreand, in the case of silicon atoms connected by siloxane bonding, thenumber of silicon atoms may amount up to about 20.

Among them, the compound having two alkenyl groups having lowpolymerizability, which is to be used for alkenyl group introduction, isselected from among compounds represented by the general formula 5:

wherein R¹ is as defined above; and R² and R⁴ each is a hydrogen atom ora methyl group and they may be the same or different.

The compound of the general formula 5 is not particularly restricted butincludes, as preferred examples in the case of R¹ being a divalenthydrocarbon group containing 1 to 20 carbon atoms, compounds mentionedbelow:

n is an integer of 1 to 20. From the viewpoint of ready raw materialavailability, however, it is preferred that n be 2, 4 or 6. Thus,1,5-hexadiene, 1,7-octadiene and 1,9-decadiene are preferred.

As for other functional group-containing olefin compounds having lowpolymerizability, alkenyl alcohols and alkenylamines are preferred.

The silyl group, which the olefin compound having low polymerizabilityhas, is not particularly restricted, but it is preferred that thecompound is represented by the formula given hereinabove in which m isequal to 0 (m=0).

In cases where amino-, hydroxy- or carboxylic acid group-containingolefin compounds having low polymerizability are to be reacted withpolymerization termini, they may be subjected to reaction as they arebut may possibly affect polymerization termini or the catalyst in someinstances. In such case, they may be used as compounds having aprotective group. As the protective group, there may be mentionedacetyl, silyl and alkoxy groups, among others.

The amount of the olefin compounds having low polymerizability to beadded for introducing such functional groups is not particularlyrestricted. The reactivity of the alkenyl group in these compounds isnot very high and it is therefore preferred that the addition amount beincreased to increase the rate of reaction. On the other hand, for costreduction, it is preferred that the addition amount be nearly equivalentto growing termini. Rationalization is therefore required depending onthe conditions.

In the case of introducing alkenyl groups into termini, the additionamount of the compound having two or more alkenyl groups having lowpolymerizability is preferably such that said compound be in excessrelative to growing polymerization termini. When the amount of saidcompound is equivalent or smaller as compared with polymerizationtermini, there may arise the possibility that both of the two alkenylgroups react with and couple together polymerization termini. In thecase of a compound having two alkenyl groups equal in reactivity, theprobability of coupling occurring is determined in a statistical mannerby the amount added in excess. A preferred addition amount is thereforenot less than 1.5 times, more preferably not less than 3 times, mostpreferably not less than 5 times.

In applying the polymer produced according to the present invention, thefunctional group introduced is utilized as it is or further subjected toconversion reaction and utilized in the form of another functionalgroup. More specifically, an alkenyl group can be converted to acrosslinkable silyl group by the hydrosilylation reaction with acrosslinkable silyl-containing hydrosilane compound. As thealkenyl-terminated vinyl polymer, those obtained by the processesalready mentioned hereinabove can all judiciously be used.

The crosslinkable silyl-containing hydrosilane compound is notparticularly restricted but includes, as typical examples, compoundsrepresented by the general formula 11:H—[Si(R¹⁹)_(2-b)(Y)_(b)O]_(m)—Si(R²⁰)_(3-a)(Y)_(a)  (11)wherein R¹⁹ and R²⁰ each represents an alkyl group containing 1 to 20carbon atoms, an aryl group containing 6 to 20 carbon atoms, an aralkylgroup containing 7 to 20 carbon atoms or a triorganosiloxy grouprepresented by (R′)₃SiO— (in which R′ is a monovalent hydrocarbon groupcontaining 1 to 20 carbon atoms and the three R′ groups may be the sameor different) and, when two or more R¹⁹ or R²⁰ groups are present, theymay be the same or different; Y represents a hydroxy group or ahydrolyzable group and when two or more Y groups are present, they maybe the same or different; a represents 0, 1, 2 or 3, b represents 0, 1or 2 and m is an integer of 0 to 19, with the condition that therelation a+mb≧1 should be satisfied.

The hydrolyzable group represented by Y is not particularly restrictedbut may be any of those known in the art. Specifically, there may bementioned a hydrogen or halogen, alkoxy, and acyloxy, ketoximate, amino,amide, acid amide, aminoxy, mercapto, alkenyloxy and like groups. Fromthe viewpoint of mild hydrolyzability and easy handling, alkoxy groupsare particularly preferred. One to three such hydrolyzable and/orhydroxy groups can be bound to one silicon atom and the total number ofhydrolyzable groups, namely a+mb, is preferably within the range of 1 to5. When two or more hydrolyzable and/or hydroxy groups are present inthis silyl group, they may be the same or different. The number ofsilicon atoms constituting this silicon group may be one, two or moreand, in the case of silicon atoms connected by siloxane bonding, thenumber of silicon atoms may amount up to about 20.

As specific examples of R¹⁹ and R²⁰ in the general formula 11, there maybe mentioned, among others, alkyl groups such as methyl and ethyl;cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl;aralkyl groups such as benzyl; and triorganosilyl groups represented by(R′)₃SiO— in which R′ is methyl, phenyl or the like.

Among such hydrosilane compounds, those hydrosilane compoundsrepresented by the general formula 12:H—Si(R²⁰)_(3-a)(Y)_(a)  (12)wherein R²⁰, Y and a are defined above, are preferred because of theirready availability.

As specific examples of the crosslinkable silyl-containing hydrosilanecompound represented by the general formula 11 or 12, there may bementioned, among others, the following:

HSiCl₃, HSi(CH₃)Cl₂, HSi(CH₃)₂Cl, HSi(OCH₃)₃, HSi(CH₃)(OCH₃)₂,HSi(CH₃)₂OCH₃, HSi(OC₂H₅)₃, HSi(CH₃)(OC₂H₅)₂, HSi(CH₃)₂OC₂H₅,HSi(OC₃H₇)₃, HSi(C₂H₅)(OCH₃)₂, HSi(C₂H₅)₂OCH₃, HSi(C₆H₅)(OCH₃)₂,HSi(C₆H₅)₂(OCH₃), HSi(CH₃)(OC(O)CH₃)₂,HSi(CH₃)₂O—[Si(CH₃)₂O]₂—Si(CH₃)(OCH₃)₂, HSi(CH₃)[O—N═C(CH₃)₂]₂ (In theabove chemical formulas, C₆H₅ denotes a phenyl group.)

In causing such a crosslinkable silyl-containing hydrosilane compound toadd to an alkenyl-terminated vinyl polymer, a hydrosilylation catalystis used. As such hydrosilylation catalyst, there can be mentionedradical initiators such as organic peroxides and azo compounds, andtransition metal catalysts.

As the radical initiator, various ones can be used without anyparticular restriction. As examples, there may be mentioned dialkylperoxides such as di-t-butyl peroxide,2,5-dimethyl-2,5-di(t-butylperoxy)hexane,2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, dicumyl peroxide, t-butylcumyl peroxide and α,α′-bis(t-butylperoxy)isopropylbenzene; diacylperoxides such as benzoyl peroxide, p-chlorobenzoyl peroxide,m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide and lauroylperoxide; peracid esters such as t-butyl perbenzoate; peroxydicarbonatessuch as diisopropyl peroxydicarbonate and di-2-ethylhexylperoxydicarboante; and peroxyketals such as1,1-di(t-butylperoxy)cyclohexane and1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane.

As the transition metal catalyst, there may be mentioned, among others,elementary platinum; solid platinum dispersed and supported on a carriersuch as alumina, silica or carbon black; chloroplatinic acid; complexesof chloroplatinic acid with alcohols, aldehydes, ketones or the like;platinum-olefin complexes and theplatinum(0)-divinyltetramethyldisiloxane complex. As examples of thecatalyst other than platinum compounds, there may be mentioned, amongothers, RhCl(PPh₃)₃, RhCl₃, RuCl₃, IrCl₃, FeCl₃, AlCl₃, PdCl₂.H₂O, NiCl₂and TiCl₄. These catalysts may be used singly or two or more of them maybe used combinedly.

As regards the catalyst amount, there are no particular restrictions. Itis recommended, however, that the catalyst be used in an amount withinthe range of 10⁻¹ to 10⁻⁸ mole, preferably 10⁻³ to 10⁻⁶ mole, per moleof the alkenyl group in the vinyl polymer. When the amount is smallerthan 10⁻⁸ mole, the curing will not proceed to a satisfactory extent.Since the hydrosilylation catalyst is expensive, it is preferred that itbe not used in excess of 10⁻¹ mole.

In cases where allyl alcohol or methallyl alcohol is used as thefunctional group-containing olefin compound having low polymerizabilityfor reaction with polymerization termini, a terminus is formed on thecarbon atoms on which an active group, such as a halogen atom, and ahydroxy group are in vicinal positions. This terminus can be convertedto an epoxy group by cyclization. The process for carrying out thiscyclization is not particularly restricted but it is preferred that analkaline compound is used for the reaction. The alkaline compound is notparticularly restricted, but there can be mentioned, among others, KOH,NaOH, Ca(OH)₂, ammonia and various amines.

Furthermore, the hydroxy group at a polymer terminus can be converted toan allyl group by condensation reaction with an allyl halide compoundsuch as allyl chloride or allyl bromide. It can also be converted to anepoxy group by a similar reaction using epichlorohydrin.

The hydroxy or amino group at a polymer terminus can be converted to acrosslinkable silyl group by reacting with a compound having acrosslinkable silyl group and a functional group capable of reactingwith the hydroxy or amino group. As the functional group capable ofreacting with the hydroxy or amino group, there may be mentioned, amongothers, halogens, carboxylic acid halide, carboxylic acid, isocyanateand like. The isocyanato group is preferred, however, from the viewpointof ready availability of appropriate compounds and of mild reactionconditions in carrying out the reaction with the hydroxy group, hencescarce decomposition of crosslinkable silyl groups.

Such crosslinkable silyl-containing isocyanate compound is notparticularly restricted but may be any of those known in the art.Specific examples are, among others, the following:

(CH₃O)₃Si—(CH₂)_(n)—NCO, (CH₃O)₂(CH₃)Si—(CH₂)_(n)—NCO,(C₂H₅O)₃Si—(CH₂)_(n)—NCO, (C₂H₅O)₂(CH₃)Si—(CH₂)_(n)—NCO,(i-C₃H₇O)₃Si—(CH₂)_(n)—NCO, (i-C₃H₇O)₂(CH₃)Si—(CH₂)_(n)—NCO,(CH₃O)₃Si—(CH₂)_(n)—NH—(CH₂)_(m)—NCO,(CH₃O)₂(CH₃)Si—(CH₂)_(n)—NH—(CH₂)_(m)—NCO,(C₂H₅O)₃Si—(CH₂)_(n)—NH—(CH₂)_(m)—NCO,(C₂H₅O)₂(CH₃)Si—(CH₂)_(n)—NH—(CH₂)_(m)—NCO,(i-C₃H₇O)₃Si—(CH₂)_(n)—NH—(CH₂)_(m)—NCO,(i-C₃H₇O)₂(CH₃)Si—(CH₂)_(n)—NH—(CH₂)_(n)—NCO (In each formula mentionedabove, n and m each is an integer of 1 to 20.)

The reaction between the hydroxy-terminated vinyl polymer and thecrosslinkable silyl-containing isocyanate compound can be carried out inthe absence or presence of any of various solvents at a reactiontemperature of 0° C. to 100° C., preferably 20° C. to 50° C. On thatoccasion, a tin catalyst and/or a tertiary amine catalyst, which is tobe mentioned later herein, can be used for promoting the reactionbetween the hydroxy group and isocyanato group.

Curable Composition

These functional group-terminated polymers can be used in curablecompositions in which various curing reactions are utilized.

The alkenyl-terminated vinyl polymer of the present invention can beused in curable compositions comprising (A) the alkenyl-terminated vinylpolymer and (B) a compound having at least two hydrosilyl groups.

The (A) component alkenyl-terminated vinyl polymer may comprise a singlespecies or a mixture of two or more species. The molecular weight of the(A) component is not particularly restricted but is preferably withinthe range of 500 to 100,000, more preferably 3,000 to 40,000. When it islower than 500, the characteristics intrinsic in the vinyl polymer canhardly be expressed. When it exceeds 100,000, a very high viscosity orlow solubility results, hence handling becomes difficult.

The (B) component compound having at least two hydrosilyl groups is notparticularly restricted but may be any of various ones. Thus, use may bemade, for example, of linear polysiloxanes represented by the generalformula 13 or 14:R²¹ ₃SiO—[Si(R²¹)₂O]_(a)—[Si(H)(R²²)O]_(b)—[Si(R²²)(R²³)O]_(c)—SiR²¹₃  (13)HR²¹ ₂SiO—[Si(R²¹)₂O]_(a)—[Si(H)(R²²)O]_(b)—[Si(R²²)(R²³)O]_(c)—SiR²¹₂H  (14)wherein R²¹ and R²² each represents an alkyl group containing 1 to 6carbon atoms or a phenyl group, R²³ represents an alkyl group containing1 to 10 carbon atoms or an aralkyl group containing 7 to 10 carbon atomsand a is an integer within the range of 0≦a≦100, b is an integer withinthe range of 2≦b≦100 and c is an integer within the range of 0≦c≦100;cyclic siloxanes represented by the general formula 15:

wherein R²¹ and R²² each represents an alkyl group containing 1 to 6carbon atoms or a phenyl group, R²³ represents an alkyl group containing1 to 10 carbon atoms or an aralkyl group containing 7 to 10 carbon atomsand d is an integer within the range of 0≦d≦8, e is an integer withinthe range of 2≦e≦10 and f is an integer within the range of 0≦f≦8, withthe condition 3≦d+e+f≦10.

These may be used singly or two or more of them may be used inadmixture. Preferred among these siloxanes from the viewpoint ofcompatibility with the vinyl polymer are phenyl-containing linearsiloxanes of the general formula 16 or 17 and cyclic siloxanes of thegeneral formula 18 or 19:(CH₃)₃SiO—[Si(H)(CH₃)O]_(g)—[Si(C₆H₅)₂O]_(h)—Si(CH₃)₃  (16)(CH₃)₃SiO—[Si(H)(CH₃)O]_(g)—[Si(CH₃){CH₂C(H)(R²⁴)C₆H₅}O]_(h)—Si(CH₃)₃  (17)wherein R²⁴ is a hydrogen atom or a methyl group, g is an integer withinthe range of 2≦g≦100 and h is an integer within the range of 0≦h≦100,and C₆H, denotes a phenyl group;

wherein R²⁴ is a hydrogen atom or a methyl group, i is an integer withinthe range of 2≦i≦10 and j is an integer within the range of 0≦j≦8, withthe condition 3≦i+j≦10, and C₆H₅ denotes a phenyl group.

Also useful as the (B) component compound having at least two hydrosilylgroups are those compounds obtained by addition reaction of ahydrosilyl-containing compound represented by one of the formulas 13 to19 to a low-molecular compound having two or more alkenyl groups withineach molecule in a manner such that the hydrosilyl group partly remainseven after the reaction. Various compounds can be used as the compoundhaving two or more alkenyl groups within each molecule. As examples,there may be mentioned hydrocarbon compounds such as 1,4-pentadiene,1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene and1,9-decadiene; ether compounds such as O,O′-diallylbisphenol A and3,3′-diallylbisphenol A; ester compounds such as diallyl phthalate,diallyl isophthalate, triallyl trimellitate and tetraallylpyromellitate; and carbonate compounds such as diethylene glycol diallylcarbonate.

Said compounds can be obtained by slowly adding the above-mentionedalkenyl-containing compound dropwise to an excess of thehydrosilyl-containing compound represented by one of the formulas 13 to19 in the presence of a hydrosilylation catalyst. Among such compounds,those illustrated below are preferred considering the ready availabilityof raw material, ease of removing the siloxane used in excess andfurther the compatibility with the (A) component polymer:

In the above formulas, n is an integer of 2 to 4 and m is an integer of5 to 10.

The polymer (A) can be mixed with the curing agent (B) in an arbitraryratio. From the curability viewpoint, however, the mole ratio betweenthe alkenyl group and hydrosilyl group is preferably within the range of5 to 0.2, most preferably 2.5 to 0.4. When said mole ratio is not lessthan 5, insufficient curing will result and only cured products havinglow strength and stickiness will be obtained. When it is less than 0.2,a large amount of the active hydrosilyl group remains in cured productseven after curing, so that cracks and voids will appear and thus uniformcured products having strength will not be obtained.

The curing reaction between the polymer (A) and curing agent (B)proceeds upon mixing of the two components and heating. For acceleratingthe reaction, however, a hydrosilylation catalyst is added. As suchhydrosilylation catalyst, all of those already mentioned hereinabove canbe used.

The crosslinkable silyl-terminated vinyl polymer of the presentinvention can be used in curing compositions comprising said polymer asa main component.

When coming into contact with moisture, the crosslinkablesilyl-terminated vinyl polymer cures by being rendered three-dimensionedas a result of a crosslinking reaction. Since the rate of hydrolysisvaries depending on the humidity, temperature and hydrolyzable groupspecies, an appropriate hydrolyzable group should be selected accordingto the use conditions.

For promoting the curing reaction, a condensation catalyst may be added.As the condensation catalyst, there may be used titanate esters such astetrabutyl titanate and tetrapropyl titanate; organotin compounds suchas dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate,stannous octoate and stannous naphthenate; lead octylate, aminecompounds such as butylamine, octylamine, dibutylamine,monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine,triethylenetetramine, oleylamine, octylamine, cyclohexylamine,benzylamine, diethylaminopropylamine, xylylenediamine,triethylenediamine, guanidine, diphenylguanidine,2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholineand 1,3-diazabicylco(5.4.6)undecene-7, and carboxylic acid saltsthereof; low-molecular polyamide resins obtained from an excess of apolyamine and a polybasic acid; reaction products obtained from anexcess of a polyamine and an epoxy compound; and amino-containing silanecoupling agents such as γ-aminopropyltrimethoxysilane andN-(β-aminoethyl)aminopropylmethyldimethoxysilane. Such known silanolcatalysts may be used singly or two or more of them may be usedaccording to need. The addition amount is preferably 0 to 10% by weightrelative to the crosslinkable silyl-terminated vinyl polymer. In caseswhere an alkoxy group is used as the hydrolyzable group Y, the use of acondensation catalyst is preferred since said polymer alone shows a slowrate of curing.

The crosslinkable silyl-terminated vinyl polymer, which is the maincomponent, when allowed to cure with a condensation catalyst added ifnecessary, can give uniform cured products. The curing conditions arenot particularly restricted but generally as follows: a temperature of 0to 100° C., preferably 10 to 50° C. and a reaction period of 1 hour toabout 1 week. A variety of cured products, from rubber-like toresin-like ones, can be produced, although the properties thereof dependon the main chain skeleton and molecular weight, among others.

The hydroxy-terminated vinyl polymer of the present invention can beused in curable compositions comprising the same as the main component.

These compositions comprise, as essential components, (A) the hydroxy-or amino-terminated vinyl polymer and (B) a compound having at least twofunctional groups capable of reacting with the hydroxy or amino group.

The (A) component hydroxy- or amino-terminated vinyl polymer may be usedsingly, or a mixture of two or more thereof can be used. The molecularweight thereof is not particularly restricted but is preferably withinthe range of 500 too 100,000. When it is smaller than 500, thecharacteristics intrinsic in the vinyl polymer can hardly be expressed.When it exceeds 100,000, a very high viscosity or low solubility willresult and handling will become difficult.

The (B) component compound having at least two functional groups capableof reacting with the hydroxy or amino group is not particularlyrestricted but includes, among others, polyisocyanate compounds havingtwo or more isocyanate groups per molecule; aminoplast resins such ashydroxymethylated melamine and alkyl ethers thereof or low condensatesthereof; polybasic carboxylic acids and halides thereof.

As the polyvalent isocyanate compound having two or more isocyanatogroups per molecule, those so far known in the art such as can be used,and for example, there can be mentioned isocyanate compounds such as2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,4,4′-diphenylmethanediisocyanate, hexamethylene diisocyanate, xylylenediisocyanate, metaxylylene diisocyanate, 1,5-naphthalenediisocyanate,hydrogenated diphenylmethanediisocyanate, hydrogenated tolylenediisocyanate, hydrogenated xylylene diisocyanate, isophoronediisocyanateand a triisocyanate such as Ipposha Yushi's B-45; biuret polyisocyanatecompounds such as Sumidur N (product of Sumitomo Bayer Urethane);isocyanurate ring-containing polyisocyanate compounds such as DesmodurIL and HL (products of Bayer A.G.) and Coronate EH (product of NipponPolyurethane); adduct polyisocyanate compounds such as Sumidur L(product of Sumitomo Bayer Urethane); and adduct polyisocyanatecompounds such as Coronate HL (product of Nippon Polyurethane). Blockedisocyanates may also be used. These may be used singly or two or more ofthem may be used combinedly.

The mixing ratio between the hydroxy- or amino-terminated polymer andthe compound having at least two isocyanato groups is not particularlyrestricted but, for example, the ratio (NCO/OH mole ratio) of theisocyanato group to the hydroxy group of the hydroxy-terminated vinylpolymer is preferably 0.5 to 3.0, more preferably 0.8 to 2.0.

For promoting the curing reaction between the hydroxy-terminated vinylpolymer and the compound having two or more isocyanato groups, a knowncatalyst, such as a organotin compound or a tertiary amine, may be addedaccording to need.

As specific examples of the organotin compound, there may be mentioned,among others, stannous octoate, dibutyltin diacetate, dibutyltindilaurate, dibutyltin mercaptides, dibutyltin thiocarboxylates,dibutyltin dimaleate, dioctyltin thiocarboxylates and the like. As thetertiary amine catalyst, there may be mentioned triethylamine,N,N-dimethylcyclohexylamine, N,N,N′,N′-tetramethylethylenediamine,N,N,N′,N′-tetramethylpropane-1,3-diamine,N,N,N′,N′-tetramethylhexane-1,6-diamine,N,N,N′,N″,N″-pentamethyldiethylenetriamine,N,N,N′,N″,N″-pentamethyldipropylenetriamine, tetramethylguanidine,triethylenediamine, N,N′-dimethylpiperazine, N-methylmorpholine,1,2-dimethylimidazole, dimethylaminoethanol, dimethylaminoethoxyethanol,N,N,N′-trimethylaminoethylethanolamine,N-methyl-N′-(2-hydroxyethyl)piperazine, N-(2-hydroxyethyl)-morpholine,bis(2-dimethylaminoethyl)ether, ethylene glycolbis(3-dimethylaminopropyl)ether and the like.

As the aminoplast resin to be used in the curable composition of thepresent invention, it is not particularly restricted but there can bementioned melamine-formaldehyde addition products (methylol compounds),melamine-formaldehyde low condensates, alkyl ethers thereof, and urearesins, among others. These may be used singly or two or more may beused combinedly. For promoting the curing reaction between thehydroxy-terminated (meth)acrylic polymer and the aminoplast resin, aknown catalyst, such as paratoluenesulfonic acid or benzenesulfonicacid, may be added.

As the polybasic carboxylic acid having at least two carboxyl groupswithin each molecule, which is to be used in the curable composition ofthe present invention, it is not particularly restricted but there canbe mentioned, among others, oxalic acid, malonic acid, succinic acid,glutaric acid, adipic acid, phthalic acid, phthalic anhydride,terephthalic acid, trimellitic acid, pyromellitic acid, maleic acid,maleic anhydride, fumaric acid, itaconic acid, like polybasic carboxylicacids and anhydrides thereof, and halides thereof. These may be usedsingly or two or more of them may be used combinedly.

When the two components (A) and (B) of the curable composition of thepresent invention are mixed up, if necessary together with a curingcatalyst, and allowed to cure, uniform cured products excellent in depthcurability can be obtained. The curing conditions are not particularlyrestricted but, generally, a temperature of 0° C. to 100° C., preferably20° C. to 80° C., is employed.

The properties of the cured products depend on the main chain skeletonsand molecular weights of the (A) component polymer and (B) componentcuring agent employed and may range widely from rubber-like ones toresin-like ones.

The epoxy-terminated vinyl polymer of the present invention can be usedin curable compositions comprising (A) the epoxy-terminated vinylpolymer and (B) a curing agent.

As (B) curing agent, various agents can be used, for example aliphaticamines, aromatic amines, acid anhydrides, and urea, melamine and phenolresins.

Applications of the cured products obtained from the curablecompositions of the present invention, such as mentioned above, arespecifically as follows: sealing materials, adhesives, pressuresensitive adhesives, elastic adhesives, paints, powder coatingcompositions, foamed products, potting agents for use in electric andelectronic fields, films, molding materials, artificial marble and soforth.

BEST MODES FOR CARRYING OUT THE INVENTION

The following specific examples illustrate this invention. They are,however, by no means limitative of the scope of this invention.

EXAMPLE 1

A 30-mL glass reaction vessel was charged with butyl acrylate (10.0 mL,8.94 g, 69.75 mmol), cuprous bromide (250 mg, 1.74 mmol),pentamethyldiethylenetriamine (0.364 mL, 302 mg, 1.74 mmol) and toluene(1 mL) and, after cooling and deaeration under vacuum, the vessel waspurged with nitrogen gas. After thorough stirring of the mixture, methyl2-bromopropionate (0.195 mL, 291 mg, 1.74 mmol) was added, and the wholemixture was stirred at 70° C. Thirty minutes later, 1,9-decadiene (1.61mL, 1.21 g, 8.72 mmol) was added and stirring at 70° C. was continuedfor 9 hours. The reaction mixture was treated with activated alumina andthe excessive portion of 1,9-decadiene (b.p. 169° C.) was distilled offwith heating under reduced pressure. The thus-obtained polymer had anumber average molecular weight of 5,300 as determined by GPC (asexpressed in terms of polystyrene equivalent) with a molecular weightdistribution of 1.41. The olefinic functional group introduction ratebased on the initiator was 0.95.

EXAMPLE 2

A 30-mL glass reaction vessel was charged with butyl acrylate (10.0 mL,8.94 g, 69.75 mmol), cuprous bromide (250 mg, 1.74 mmol),pentamethyldiethylenetriamine (0.364 mL, 302 mg, 1.74 mmol) and toluene(1 mL) and, after cooling and deaeration under vacuum, the vessel waspurged with nitrogen gas. After thorough stirring of the mixture, methyl2-bromopropionate (0.195 mL, 291 mg, 1.74 mmol) was added, and the wholemixture was stirred at 70° C. Forty-five minutes later, 1,5-hexadiene(1.01 mL, 0.70 g, 8.72 mmol) was added and stirring at 70° C. wascontinued for 8 hours. The reaction mixture was treated with activatedalumina and the excessive portion of 1,5-hexadiene was distilled offwith heating under reduced pressure. The thus-obtained polymer had anumber average molecular weight of 4,800 as determined by GPC (asexpressed in terms of polystyrene equivalent) with a molecular weightdistribution of 1.33. The olefinic functional group introduction ratebased on the initiator was 0.71.

EXAMPLE 3

A 100-mL glass reaction vessel was charged with butyl acrylate (50.0 mL,44.7 g, 0.349 mol), cuprous bromide (1.25 g, 8.72 mmol),pentamethyldiethylenetriamine (1.82 mL, 1.51 g, 8.72 mmol) andacetonitrile (5 mL) and, after cooling and deaeration under vacuum, thevessel was purged with nitrogen gas. After thorough stirring of themixture, diethyl 2,5-dibromoadipate (1.57 g, 4.36 mmol) was added, andthe whole mixture was stirred at 70° C. Sixty minutes later,1,7-octadiene (6.44 mL, 4.80 g, 43.6 mmol) was added and stirring at 70°C. was continued for 2 hours. The reaction mixture was treated withactivated alumina and the volatile matter was distilled off with heatingunder reduced pressure. The product was dissolved in ethyl acetate andthe solution was washed with 2% hydrochloric acid and brine. The organiclayer was dried over Na₂SO₄ and the volatile matter was distilled offwith heating under reduced pressure, to give an alkenyl-terminatedpolymer. The polymer obtained had a number average molecular weight of13,100 as determined by GPC (as expressed in terms of polystyreneequivalent) with a molecular weight distribution of 1.22. The olefinicfunctional group introduction rate based on the number average molecularweight was 2.01.

EXAMPLE 4

The alkenyl-terminated poly(n-butyl acrylate) (30.5 g) obtained inExample 3 and an equal amount of aluminum silicate (Kyowaad 700 PEL;product of Kyowa Chemical) were mixed together in toluene and themixture was stirred at 100° C. Four hours later, the aluminum silicatewas filtered off and the volatile matter was distilled off with heatingunder reduced pressure to purify the polymer.

A 200-mL glass-made pressure reaction vessel was charged with the abovepolymer (23.3 g), dimethoxymethylhydrosilane (2.55 mL, 20.7 mmol),dimethylorthoformate (0.38 mL, 3.45 mmol) and a platinum catalyst. Theplatinum catalyst was used in a mole ratio of 2×10⁻⁴ equivalentsrelative to the alkenyl group in the polymer. The reaction mixture washeated at 100° C. for 3 hours. The volatile matter was distilled offfrom the mixture to give a crosslinkable silyl-terminated poly(n-butylacrylate). The number of silyl groups introduced per oligomer moleculewas 1.41 as determined by ¹H-NMR analysis.

EXAMPLE 5

The silyl-terminated poly(butyl acrylate) obtained in Example 4,dibutyltin dimethoxide and water were mixed up. The tin catalyst andwater were used each in an amount of 1 weight part relative to thepolymer.

The thus-obtained composition was poured into a mold, deaerated underreduced pressure and heated at 50° C. for 20 hours for curing, to give asheet-like cured product having rubber elasticity. The cured product wasimmersed in toluene for 24 hours and the gel fraction was determinedbased on the change in weight between before and after immersion andfound to be 85%.

Dumbbell test specimens (No. 2(1/3)) were punched out from thesheet-like cured product and subjected to tensile testing using aShimadzu autograph (measurement conditions: 23° C., 200 mm/min). Thestrength at rupture was 0.34 MPa and the elongation at rupture was 86%.

EXAMPLE 6

In a 500-mL three-necked flask equipped with a reflux condenser, n-butylacrylate (300 mL) was polymerized in a nitrogen atmosphere at 70° C.using cuprous bromide (1.50 g, 10.5 mmol) as the catalyst,pentamethyldiethylenetriamine (1.65 mL) as the ligand, diethyl2,5-dibromoadipate (9.42 g, 26.2 mmol) as the initiator and acetonitrile(30 mL) as the solvent. At the time point when the percentpolymerization of n-butyl acrylate amount to 93%, 1,7-octadiene (38.6mL, 0.261 mol) was added and the resulting mixture was heated at thesame temperature. The reaction product was diluted with ethyl acetate,the dilution was passed through an activated alumina column to therebyremove the catalyst, and the volatile matter was distilled off withheating under reduced pressure to give an alkenyl-terminated polymer.The polymer had a number average molecular weight of 13,800 asdetermined by GPC (as expressed in terms of polystyrene equivalent) witha molecular weight distribution of 1.28. The number of alkenyl groupsintroduced per oligomer molecule was 1.84 as determined by ¹H-NMRanalysis.

EXAMPLES 7 TO 9 Production of Cured Products

The alkenyl-terminated polymer obtained in Example 6 was treated withaluminum silicate (Kyowaad 700 PEL; product of Kyowa Chemical) to removethe trace impurities in the polymer.

Then, the purified poly(acrylic ester) was mixed up with a polyvalenthydrogensilicone compound and the complex of platinum having a valencyof 0 with 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (8.3×10⁻⁸ mol/Lsolution in xylene; 7.0×10⁻³ mole equivalent relative to the alkenylgroup). The polyvalent hydrogensilicone compound used was the compoundS-1 illustrated below (SiH value: 7.72 mmol/g) (Example 7), the compoundS-2 illustrated below (SiH value: 9.81 mmol/g) (Example 8) or partiallyα-methylstyrene-modified methylhydrogensiloxane S-3 (SiH value: 7.69mmol/g) (Example 9). The amount of the polyvalent hydrogensiliconecompound used was such that the mole ratio between the alkenyl group inthe polymer and the SiH group of the hydrogensilicone compound amountedto 1/1.2 to 1/1.5.

A portion of each of the thus-obtained compositions was subjected to acuring test on a hot plate maintained at 130° C. and the gelling timewas measured. The remaining portion of each composition was deaeratedunder reduced pressure and poured into a mold and subjected to curingunder heating. Heating at 100° C. gave a rubber-like cured product. Thecomposition cured in 15 seconds in Example 7, 21 seconds in Example 8and 26 seconds in Example 9.

EXAMPLE 10 Hydroxy Group Introduction by Addition of Pentenol

In a nitrogen atmosphere, a 100-mL glass reaction vessel was chargedwith cuprous bromide (0.500 g, 3.49 mmol), acetonitrile (5 mL),butylacrylate (50.0 mL, 44.7 g, 0.349 mol), diethyl 2,5-dibromoadipate(1.57 g, 4.36 mmol) and pentamethyldiethylenetriamine (0.103 mL, 0.0855g, 0.493 mmol) and the mixture was stirred at 70° C. for 150 minutes. Atthat time, the consumption of butyl acrylate was 98% as determined by GCanalysis. Immediately, 4-pentenol (2.70 mL, 2.25 g, 0.0261 mol) wasadded, and stirring was further continued at 70° C. for 270 minutes. Themixture was treated with activated alumina and the volatile matter wasdistilled off with heating under reduced pressure to give ahydroxy-terminated polymer. The polymer obtained had a number averagemolecular weight of 12,600 as determined by GPC (as expressed in termsof polystyrene equivalent) with a molecular weight distribution of 1.22.The hydroxy group introduction rate was 1.3 as determined based on thenumber average molecular weight.

EXAMPLE 11 Epoxy Group Introduction by Addition of Allyl Alcohol

In a nitrogen atmosphere, a 100-mL glass reaction vessel was chargedwith cuprous bromide (0.500 g, 3.49 mmol), acetonitrile (5 mL),butylacrylate (50.0 mL, 44.7 g, 0.349 mol), diethyl 2,5-dibromoadipate(1.57 g, 4.36 mmol) and pentamethyldiethylenetriamine (0.0910 mL, 0.0755g, 0.436 mmol) and the mixture was stirred at 70° C. for 180 minutes. Atthat time, the consumption of butyl acrylate was 94% as determined by GCanalysis. Immediately, allyl alcohol (1.78 mL, 1.52 g, 0.0262 mol) wasadded, and stirring was further continued at 70° C. for 300 minutes. Themixture was treated with activated alumina and the volatile matter wasdistilled off with heating under reduced pressure. The polymer obtainedhad a number average molecular weight of 11,300 as determined by GPC (asexpressed in terms of polystyrene equivalent) with a molecular weightdistribution of 1.2. This was heated in refluxing pyridine and then thevolatile matter was distilled off with heating under reduced pressure.The epoxy group introduction was confirmed by ¹H-NMR analysis of theoligomer obtained.

EXAMPLE 12 Silyl Group Introduction by Addition of an Octenylsilane

In a nitrogen atmosphere, a 100-mL glass reaction vessel was chargedwith cuprous bromide (1.00 g, 6.98 mmol), acetonitrile (5 mL), (50.0 mL,44.7 g, 0.349 mol), diethyl 2,5-dibromoadipate (1.57 g, 4.36 mmol) andpentamethyldiethylenetriamine (0.0910 mL, 0.0755 g, 0.436 mmol) and themixture was stirred at 70° C. for 180 minutes. At that time, theconsumption of butyl acrylate was 87% as determined by GC analysis.Immediately, 8-dimethoxymethylsilyl-1-octene (9.43 g, 0.0436 mol) andpentamethyldiethylenetriamine (0.273 mL, 0.226 g, 1.31 mmol) were added,and stirring was further continued at 70° C. for 390 minutes. Themixture was treated with activated alumina and the volatile matter wasdistilled off with heating under reduced pressure to give asilyl-terminated polymer. The polymer obtained had a number averagemolecular weight of 14,700 as determined by GPC (as expressed in termsof polystyrene equivalent) with a molecular weight distribution of 1.35.¹H-NMR analysis revealed quantitative and stable terminal silyl groupintroduction.

EXAMPLE 13 Condensation Type Curing

The silyl-terminated poly(butyl acrylate) obtained in Example 12 wasmixed up with dibutyltin dimethoxide and water. The tin catalyst andwater were used each in an amount of 1 weight part relative to thepolymer.

The thus-obtained composition was deaerated under reduced pressure andthen heated at 50° C. for curing, to give a cured product having rubberelasticity. The cured product was immersed in toluene and the gelfraction was calculated to be 99% from the change in weight betweenbefore and after immersion.

INDUSTRIAL APPLICABILITY

The functional group-terminated vinyl polymer of the present invention,in which the terminal group is bound to the main chain via carbon-carbonbonding and therefore is stable and in which the terminal structure hasthe functional group introduced in a well controlled manner, is usefulin applying it in curable compositions, among others. According to theproduction process of the present invention, it is possible to producepolymers having any of various functional groups at a terminus with easeby adding a compound which has olefin group having low polymerizabilityand various functional group to various vinyl monomer polymerizationsystems.

1. An allyl-terminated polymer as produced by reacting ahydroxy-terminated polymer with an allyl halide, wherein thehydroxyl-terminated polymer has, at a molecular chain terminus, astructure represented by the general formula 1:

wherein R³ is a hydroxyl group, R¹ is a divalent hydrocarbon groupcontaining 1 to 20 carbon atoms or a group having a structurerepresented by the general formula 3:

in which R⁵ is an oxygen atom, a nitrogen atom or an organic groupcontaining 1 to 20 carbon atoms, R⁶ is a hydrogen atom or a methyl groupand each may be the same or different, and R² is a hydrogen atom or amethyl group and X is a halogen atom, a nitroxide or sulfide group or acobalt porphyrin complex.
 2. A crosslinkable silyl-terminated polymer asproduced by reacting an alkenyl-terminated polymer with a crosslinkablesilyl-containing hydrosilyl compound, wherein the alkenyl-terminatedpolymer has, at a molecular chain terminus, a structure represented bythe general formula 1:

wherein R³ is a group represented by the general formula 2:

in which R⁴ represents a hydrogen atom or a methyl group, R¹ is—(CH2)_(n)—, —CH(CH₃)—, —CH(CH₂CH₃)—, —C(CH₃)₂—, —C(CH₃)(CH₂CH₃)—,—C(CH₂CH₃)₂— or —CH₂CH(CH₃)—, wherein n is an integer of 1 to 20, and R²is a hydrogen atom or a methyl group and X is a halogen atom, anitroxide or sulfide group or a cobalt porphyrin complex.
 3. Acrosslinkable silyl-terminated polymer as produced by reacting ahydroxy- or amino-terminated polymer with a compound having acrosslinkable silyl group and a functional group capable of reactingwith the hydroxy or amino group, wherein the hydroxyl- oramino-terminated polymer has, at a molecular chain terminus, a structurerepresented by the general formula 1:

wherein R³ is a hydroxyl or amino group, R¹ is a divalent hydrocarbongroup containing 1 to 20 carbon atoms or a group having a structurerepresented by the general formula 3:

in which R⁵ is an oxygen atom, a nitrogen atom or an organic groupcontaining 1 to 20 carbon atoms, R⁶ is a hydrogen atom or a methyl groupand each may be the same or different, and R² is a hydrogen atom or amethyl group and X is a halogen atom, a nitroxide or sulfide group or acobalt porphyrin complex.
 4. An epoxy-terminated polymer as produced byreacting a hydroxy-terminated polymer with epichlorohydrin, wherein thehydroxyl-terminated polymer has, at a molecular chain terminus, astructure represented by the general formula 1:

wherein R³ is a hydroxyl group, R¹ is a divalent hydrocarbon groupcontaining 1 to 20 carbon atoms or a group having a structurerepresented by the general formula 3:

in which R⁵ is an oxygen atom, a nitrogen atom or an organic groupcontaining 1 to 20 carbon atoms, R₆ is a hydrogen atom or a methyl groupand each may be the same or different, and R² is a hydrogen atom or amethyl group and X is a halogen atom, a nitroxide or sulfide group or acobalt porphyrin complex.
 5. A curable composition which comprises (A)an alkenyl-terminated polymer and (B) a compound having at least twohydrosilyl groups, wherein the alkenyl-terminated polymer has, at amolecular chain terminus, a structure represented by the general formula1:

wherein R³ is a group represented by the general formula 2:

in which R⁴ represents a hydrogen atom or a methyl group, R¹ is—CH₂)_(n)—, —CH(CH₃)—, —CH(CH₂CH₃)—, —C(CH₃)₂—, —C(CH₃) (CH₂CH₃)—,—C(CH₂CH₃)₂— or —CH₂CH(CH₃)—, wherein n is an integer of 1 to 20, and R²is a hydrogen atom or a methyl group and X is a halogen atom, anitroxide or sulfide group or a cobalt porphyrin complex.
 6. A curablecomposition which comprises (A) a hydroxyl- or amino-terminated polymerand (B) a compound having at least two functional groups capable ofreacting with the hydroxyl or amino group, wherein the hydroxyl- oramino-terminated polymer has, at a molecular chain terminus, a structurerepresented by the general formula 1:

wherein R³ is a hydroxyl or amino group, R¹ is a divalent hydrocarbongroup containing 1 to 20 carbon atoms or a group having a structurerepresented by the general formula 3:

in which R⁵ is an oxygen atom, a nitrogen atom or an organic groupcontaining 1 to 20 carbon atoms, R⁶ is a hydrogen atom or a methyl groupand each may be the same or different, and R² is a hydrogen atom or amethyl group and X is a halogen atom, a nitroxide or sulfide group or acobalt porphyrin complex.
 7. The curable composition according to claim6, wherein the component (B) is a polyvalent isocyanate.
 8. A curablecomposition which comprises a crosslinkable silyl-terminated polymerproduced according to claim 2 as a main component.
 9. A curablecomposition which comprises a crosslinkable silyl-terminated polymeraccording to claim 3 as a main component.
 10. A curable compositionwhich comprises (A) an epoxy-terminated polymer according to claim 4 and(B) a curing agent for epoxy resins.